Synthesis of (sub)microcrystals of dinuclear terbium(III) carboxylate (Hpiv)6Tb2(piv)6 and polymeric terbium(III) carboxylate {Tb(piv)3}n in supercritical carbon dioxide. Photoluminescence and magnetic properties

• Published in: The Journal of supercritical fluids 2019-12, Vol.154, Article 104611
• Main Authors: Fomina, I.G., Mishakov, G.V., Krotova, L.I., Popov, V.K., Bagratashvili, V.N., Bogomyakov, A.S., Zavorotny, Yu. S., Eremenko, I.L.
• Format: Article
• Language: English
• Subjects: Luminescence properties; Magnetic properties; Micronization; Polymerization; Supercritical carbon dioxide
• ISSN: 0896-8446
• DOI: 10.1016/j.supflu.2019.104611

[Display omitted] •Coordination polymer {Tb(piv)3}n was prepared from complex (Hpiv)6Tb2(piv)6 by sc-CO2 processing.•Terbium carboxylates was prepared as single-phase (sub)microcrystals with a controlled size.•Polymer {Tb(piv)3}n can be prepared as polycrystalline aggregates with different morphologies.•Size of aggregates affects the photoluminescent and magnetic properties of terbium carboxylates. Supercritical fluid micronization by rapid expansion of supercritical solutions setup using supercritical carbon dioxide as a fluid and the dinuclear complex (Hpiv)6Tb2(piv)6 (1) as the starting compound allows the preparation of either the single-phase dinuclear complex (Hpiv)6Tb2(piv)6 (1a) or the coordination polymer {Tb(piv)3}n (2a, 2b, 2c) as (sub)microcrystals with a controlled size depending on the processing parameters. It was shown that {Tb(piv)3}n (2) can in principle be synthesized by supercritical carbon dioxide processing as polycrystalline particles with different morphologies. A decrease in the size of polycrystalline particles (aggregates) of 1 and 2 and an increase in the fraction of defects in the crystal structure, respectively, lead to an increase in the degree of photoluminescence quenching at these defects and a change in magnetic properties of 1.